Textile decorating emulsion



Patented June 17, 1952 UNITED STATES PTENT OFFICE TEXTILE DECORATINGEMULSION Olive-Sue Linkletter, Englewood, N. J assignor to InterchemicalCorporation, New York, N. Y.,

a corporation of Ohio No Drawing. Application May 25, 1951,-

, Serial No. 228,371

and alkali-resistance.

Compositions comprising an aqueous medium, usually water, emulsified asthe inner phase in an outer lacquer phase containing a film-formingbinder, generally an organic solvent-soluble thermosetting resin, havegone into extensive use in the printing and the dyeing of textiles andsimilar fabrics. A pigment may be dispersed in the lacquer phase of suchan emulsion: the application of such a pigmented water-in-lacqueremulsion in the printing of textile fabrics is disclosed in Jenett,2,222,581 and 2,222,582 and in the dyeing of textile fabrics in Cassel,2,248,696. Alternatively, a water-soluble dyestuff of dyestuif componentmay be dissolved in the aqueous phase of such an emulsion: theapplication of such a colored emulsion in the decoration of textilefabrics is described in Cassel, 2,202,283.

Alkyd resins of the glycerol-phthalate type are customarily included inthe lacquer phase of such an emulsion, not only because of theirfilm-forming properties but also because'oi their emulsifyingcharacteristics. Such an alkyd resin can be used as the solefilm-forming material in the lacquer phase, particularly'of an emulsionof low solids content. It can also be used in conjunction with otherfilm-forming materials such as thermosetting resins, the emulsions ofwhich are not notably stable, in order to impart stability thereto. Theuse of these alkyd resins leaves much to be desired with respect tolongtime stability cf such emulsions, however; and, moreover, theresulting decorated fabric generally does not possess entirelysatisfactory fastness to washing and scrubbing and satisfactoryresistance to alkali.

I have now discovered that unusually stable water-in-lacquertextile-decorating emulsions can be prepared by utilizing, as aningredient thereof, an alkyd resin comprising the reaction product of(1) an adduct of an alpha-unsaturated dicarboxylic acid and a terpeneand (2) a partial ester of pentaerythritol with the conjointpolymerization product of styrene and dehydrated castor oil. Not onlydoes this particular type of film-forming alkyd resin possessexceptionally good emulsification properties; but a fabric decoratedtherewith exhibits an improved fastness to washing and an excellentresistance to the action of alkali.

The styrene-dehydrated castor oil conjoint polymerization productforming the basis of the alkyd resin utilized in carrying out thepresent invention can be prepared in any desired manner. A satisfactorycopolymer of this type can be prepared by heating a mixture of styreneand dehydrated castor oil in the desired proportions in the presence ofa peroxide catalyst and of a mercaptan polymerization-modifier, asdescribed in the copending application of C. J. Opp and R. E. Werner, S.N. 713,931, filed December 4, 1946, now U. S. Patent No. 2,574,753.

The present alkyd is prepared by heating such a conjoint polymer withpentaerythritol desirably in the presence of an alkaline catalyst toeffect a partial alcoholysis of the former and then in turn esterifyingthe resulting partial ester by heating an adduct of an alpha-unsaturateddicarboxylic acid and a terpene therewith.

Alternatively, the copolymer can be heated with the pentaerythritol andthe adduct in a single cook to form the alkyd resin. Full details of thepreparation of this type of alkyd are contained in the copendingapplication of C. P. Opp and R. E. Werner, S. N. 713,932, filed December4, 1946, now U. S. Patent No. 2,560,592.

For the best emulsification and for satisfactory washfastness in theresulting decorated textile, the ratio of styrene of dehydrated castoroil in the conjoint polymer should range from about to 50 parts byweight of styrene to about 70 to 50 parts by weight-of dehydrated castoroil. When a lower or a higher ratio of styrene to dehydrated castor oilis employed in the preparation of this copolymer, thenthe degree ofwashfastness of the decorated fabric begins to decrease to too great anextent. Excellent emulsification accompanied by excellent washfastnessof the decorated textile is obtained when the conjoint polymer isprepared from about 40 parts by weight of styrene and about parts byweight of dehydrated castor oil.

The ratio of pentaerythritol to such conjoint polymer may vary from aminimum of 0.5:1 to a maximum of about 1:1 on a molar basis. Thisminimum ratio represents the least amount of pentaerythritol that can bereacted with one mol of the conjoint polymer, the resulting partialester still theroetically having two free hydroxyl groups foresterification with the unsaturated dibasic acid-terpene adduct. If themolar ratio is greater than the indicated maximum, then the reactionmixture, upon addition of the dibasic acid-terpene adduct, gels toofast; and the resulting alkyd has too high an acid number and can not beused for present purpose.

A sufficient amount of the unsaturated dibasic acid-terpene adductshould be esterified with the partial ester of pentaerythritol with suchconjoint polymer that the final alkyd resin has a theoretical freehydroxy percentage ranging from about 0.5 to 3 and a maximum acid numberof about 25. Below about 0.5% theoretical free hydroxyl, the alkydgenerally possesses unsatisfactory emulsifying properties. Above about3% theoretical free hydroxyl, the washfastness of the resultingdecorated fabric is generally poor. If the alkyd has an acid number muchabove about 25, then the textile-decorating emulsions, especially thosecontaining a thermosetting resin such as organic solvent-solublemelamineformaldehyde resin, tend to be unstable and to gel rapidly. Iprefer, generally, to carry out the reaction until the alkyd has an acidnumber of about 20 to about 25.

This dibasic acid-terpene adduct'can be pre-' pared by condensing in theknown manner an alpha-unsaturated dicarboxylic acid with a terpene. Atypical alpha-unsaturated dicarboxylic acid suitable for this purposecomprises maleic acid. Other acids such as fumaric acid, citraconicacid, and itaconic acid can also be used, however; and the anhydrides ofthese acids can beu sed in place of the acids themselves, the anhydridesbeing the equivalent of the acids for this purpose. The terpene maycomprise a straight-chain terpene containing a conjugated system ofdouble bonds, a monocyclic terpene whether or not its double bonds areconjugated, a'bicyclic terpene, and the like.

As is well known, the nature of'the adduct depends on the type ofterpene utilized and the manner in which the reaction is carried out.For example, the reaction between a monocyclic terpene containing aconjugated system of double bonds and a' suitable dibasic acid resultsin an adduct comprising a mixture of a Diels-Alder reaction product anda polymeric material. A monocyclic terpene whose pair of double bonds isnot conjugated and the anhydride of a dibasic acid react, in thepresence of an acid, to give a mixture of the Diels-Alder reactionproduct and thepolymeric material, the terpene rapidly isomerizing toalpha-terpinene. In the absence of acid, however, these same reactantsresult in a mixture comprising an addition product of a different typeand an interpolymerization product.

Generally, the terpene and the dibasic acid are reacted in approximatelyequimolar proportions although other ratios can also be employed. Adescription of the preparation of these dibasic acid-terpene adducts isgiven at pages 843 to 846 of Carleton Ellis The Chemistry of SyntheticResins (Reinhold Publishing Corporation, New York, 1935), to which aswell'as to the patents mentioned therein reference is made for furtherdetails. Anyof'these'adducts, all of which are essentially polybasicacids, can be used in the production of the present'styrene-castor oilcopolymer'alkyd. Adducts of this type are available c'ommercially underthe trade name of Petrex acids.

The partial ester should be cooked with the dibasic acid-terpene adduct(or the mixture of copolymer, pentaerythritol, and adduct should becooked) until the resulting alkyd has a. maximum gel time of about 25'seconds. (This gel time is the time in seconds required for a thin filmof' the alkyd resin spread on a plate maintained at a constanttemperature 190 C. to gel or cure.) A loss in color value of thedecorated fabric becomes apparent if the gel time of the alkyd is muchabove about 25 seconds. Generally; we prefer to heat the reactionmixture until thealkyd has a gel time of about 15 to about 25 seconds.

Where the copolymer is prepared in accordance with the disclosure in thecopending application of Opp and Werner, S. N. 713,931, the mixture ofstyrene and dehydrated castor oil is heated to a temperaturepreferablynot in excess of about 275 to 300 C. in the presence of asuitable peroxide catalyst such as tertiary butyl hydrop'e'roxide,lauryl peroxide, and the like and of a mercaptan, especially an alkylmercaptan, until the reaction has been carried to the desired extent.The peroxide catalyst should be present in a catalytic amount, and themercaptan is advantageously present in an amount ranging from about 0.5to 5% of the weight of the styrene. The reaction of the copolymer withthe pentaerythritol is efiected by heating to a temperaturenotsubstantiallyin excess of about 230 C. until the desired extent ofreaction has been accomplished; and the reaction of the resultingpartial ester with,the adduct is similarly effected by heating until theresulting alkyd has the desired acid number and gel time. Desirably,each reaction is carried out in the presence of an inert gas such ascarbon dioxide so that products of a lighter color are obtained.

The preparation of alkyd resins suitable for use in carrying out thepresent invention is illustrated by the following examples:

Example A In a flask, equipped with a stirrer, a reflux condenser and atrap for the removal of water, are placed 600 parts (40%) of styrene and900 parts (60%) of dehydrated castor oil (all parts by weight in thisand other examples) together with about 16 parts of tertiary butylhydroperoxide and about 12 parts of tertiary butyl mercaptan. Thismixture is heated to a temperature of about 260 C. and is maintained atthis temperature until the viscosity of the resulting styrene-dehydratedcastor oil copolymer is about 377 poises at 30 C.

568 parts (1 mol) of this 40-60 styrene-dehydrated castor oil copolymerare cooled to about C. and '73 parts (0.54 mol) of pentaerythritol areadded thereto over a period of 15 to 20 minutes. A trace of calciumoxide is added to catalyze the esterification. The mixture is thenheated to 230? C. and is maintained at this temperature with agitationfor about 1 /2 hours, or until the reaction product is clear when it isfirst flowed out on glass.

This partial ester is cooled to about 205 C. and 168 parts (0.78 mol) ofPetrex acid (a terpene-maleic anhydride adduct) are added thereto. Themixture is then heated to 230 C. over a period of half an hour andis-maintained at this temperature until the reaction product has a geltime of 20 to 25 seconds on a cure plate maintained at a constanttemperature of C. The resulting alkyd resin, which has a free hydroxylpercentage of about 0.9 and'an acid number of 24 to 26, is reduced to50% solids'by the addition of Solvesso 100 (highly aromatic solventnaphtha having a boiling range of 310 F. to 365 F.) thereto.

Example B An alkyd of substantially similar suitability can be-preparedby replacing the 568 parts of'the 40-60 styrene dehydrated castor oilcopolymer of Example A with 491 parts (1 mol) of a 50-50styrene-dehydrated castor oil copolymer prepared in the same manner.

Example C 646 parts-(1 mol) of a 30-70 styrene-dehydrated'castor oilcopolymer can be substituted for the 568 parts of the 40-60styrene-dehydrated castor oil copolymer of Example A, and an alkydlfiseful for the present purpose prepared thererom.

Example D A vehicle concentrate is prepared by mixing together thefollowing ingredients:

50% solids solution of Example A 40 Solvesso #100 (highly aromaticsolvent naphtha having a boiling range of 310 to 365 F.) 20- andemulsifying into the resulting lacquer:

% aqueous solution of diammonium 7 phosphate 30 Water 10 The resins ofExamples B to D can be similarly formulated into vehicle concentrates.

This vehicle concentrate can be thinned or cut by the addition offurther organic solvent thereto and the emulsiflcation of further waterthereinto in the proportions necessary to give a textiledecoratingvehicle having the body and the viscosity desired:

Emamplell A textile-decorating vehicle or clear having a solids contentof 1% is prepared from the following ingredients:

Vehicle concentrate of Example I 5 Mineral spirits 20 Water 75 Theresulting emulsion is unsually stable and retains its stability for aprolonged period of time.

Example III A textile-decorating vehicle or clear having a solidscontent of 0.4% is prepared from the following ingredients:

Vehicle concentrate of Example I 2 Mineral spirits 23 Water 75 Thiswater-in-lacquer emulsion i also unusually stable.

The solution of the alkyd resin can also be out directly to form such aclear:

Example IV A clear having a solids content of 1% is prepared by mixingthe following:

50%solids resin solution of Example A 2 Mineral spirits 23 andemulsifying into the resulting lacquer:

10% aqueous solution of diammonium phosphate 5 Water 70Textile-decorating compositions can be prepared from such vehicles orclears by mixing a color-concentrate containing a pigment or awater-soluble dyestuff therewith. The proportions in which therespective color concentrate and the respective vehicle are mixeddepend, of

6 course. on the depth of shade desired in the finished fabric. Typicaltextile-decorating compositions are illustrated by the followingexamples:

' Example 1 A pigmented color concentrate or ink comprising awater-in-lacquer emulsion consisting of the following ingredients:

Pigment Organic solvent-soluble urea-formaldehyde ormelamine-formaldehyde resin 9 to 30 Fatty acid (to disperse the pigmentand the resin) 1 Water 1 Up to 10 Solvesso #100, turpentine and/or pineoil Balance Example 2 A textile-decorating composition containing aWater-soluble dyestuff in the aqueous phase is prepared by mixingtogether the following:

50% solids resin solution of Example A 2 Mineral spirits 48 andemulsifying into the resulting lacquer: I

10% aqueous solution of a water-soluble dye or dyestuif component 40Water The color strength can be varied by changing the proportion ofaqueous dyestuif solution.

Compared with the customary glycerol-phthalate type of alkyd, thepresent alkyd resin produces emulsions that possess far superiorstability and that remain stable for far longer periods of time. Thecolored water-in-lacqu'er emulsions containing the present alkyd aresimilarly far more stable and remain usable (printable or dyeable) for amuch longer period of time than the same type of emulsions formulatedfrom the ordinary glycerol-phthalate alkyd. The resistance of a fabricdecorated with the present alkyd-containing emulsion to washing andespecially to the action of alkali is definitely superior to that of afabric decorated with the usual glycerol-phthalate alkyd-containingemulsion.

The present alkyd exhibits a similar superiority for use inwater-in-lacquer textile-decorating emulsions even over similarlyprepared alkyds such as that in which phthalic acid is used in place ofthe adduct of an alpha-unsaturated dicarboxylic acid and a terpene. Inparticular, the present specific type of alkyd is especiallycharacterized by its superior emulsification properties and by thesuperior alkali-resistance exhibited by a fabric decorated with anemulsion containing it. The finished fabric, in addition, possesses animproved color value.

Moreover, the present alkyd has excellent compatibility with ethylcellulose, a film-forming material often incorporated in the lacquerphase of a water-in-lacquer textile-decorating emulsion. Emulsionscontaining both the present alkydz and ethyl cellulose possessexcellentrhem. logical-properties and produce decorated fabrics havingabetter color value than that'obtained when ethyl cellulose is usedalone.

Although unusually stable water-in-lacquer emulsions can be preparedfrom the present alkyd, satisfactory lacquer-in-water emulsionsvaporizable water-immiscible organic solvent,

containing, as an emulsifying film-forming material, an alkyd resincomprising the reaction product of (1) and adduct of analpha-olefinically unsaturated dicarboxylic acid and a terpene and (2)an alcoholysis product of 0.5 to 1 mol of pentaerythritol with 1 mol ofthe conjoint polymerization product of about 30 to 50 parts by weight ofstyrene and '70 to 50 parts by weight of dehydrated castor'oil, saidalkyd resin having a free hydroxyl percentage ranging from 0.5 to 3; amaximum acid number on the order of 25, and a maximum gel time on theorder of 25 seconds on a cure plate maintained at a temperature of 190C., and being soluble in said organic solvent.

2.- A'water-in-lacquer textile-decorating emulsion, the lacquer phase ofwhich comprises a vaporizable water-immiscible organic solventcontaining, as an emulsifying film-forming material, an alkyd resincomprising the reaction product of (1) an adduct of analpha-olefinically unsaturated dicarboxylic acid and a terpene and (2)an alcoholysis product of 0.5 to 1 mol of pentaerythritol with 1 mol ofthe conjoint poly- 8': merization product of 40 parts by weight ofstyrene and 60 parts by weight of dehydrated castor oil, said alkydresin having a free'hydroxyl percentage'ranging from 0.5 to 3, amaximumacidnumber 'on the order of-25. and a maximum gel time" on the order'ofseconds on a' cure platemaintained at atemperature of 190C; and beingsoluble in said organic-solvent;

3. The textile-decorating emulsion asclaimed inclaim 2, inwhich thealpha-unsaturated dicarboxylicacid comprises maleic acid.

4. A water-in-lacquer textileedecorating-emulsion, the lacquer phase ofwhich comprises a solution of a thermo-setting synthetic resin in avaporizable water-immiscible organic. solvent containing, as anemulsifyingfilm-forming material, an alkyd resin comprising the reactionproduct of. (1) an adduct of. maleic acid and a;

terpene and. (2) an alcoholysis; product of--0.5:

to 1 mol of pentaerythritol with 1 mol-of-the conjoint polymerizationproduct of 40 parts-by weight of styrene and parts by weight ofdehydrated'castor oil, said alkyd resin having a" free hydroxylpercentage ranging from 0.5 to 3, a maximum acid number on the orderof'25, anda maximum gel timeonthe order of 25seconds on a cure platemaintained at a temperature of C., and being soluble in said organicsolvent. V g p OLIVE-SUE LINKLETTER."

REFERENCES CITED The following references are of record inthe file ofthis patent:

UNITED STATES PATENTS Name" Number Date Bloch -Oct. 5, 1948"

1. A WATER-IN-LACQUER TEXTILE-DECORATING EMULSION, THE LACQUER PHASEORGANIC COMPRISES A VAPORIZABLE WATER-IMMISCIBLE ORGANIC SOLVENTCONTAINING, AS AN EMULSIFYING FILM-FORMING MATERIAL, AN ALKYD RESINCOMPRISING THE REACTION PRODUCT OF (1) AND ADDUCT OF ANALPHA-OLEFINICALLY UNSATURATED DICARBOXYLIC ACID AND A TERPENE AND (2)AN ALCOHOLYSIS PRODUCT OF 0.5 TO 1 MOL OF PENTAERYTHRITOL WITH 1 MOL OFTHE CONJOINT POLYMERIZATION PRODUCT OF ABOUT 30 TO 50 PARTS BY WEIGHT OFSTYRENE AND 70 TO 50 PARTS BY WEIGHT OF DEHYDRATED CASTOR OIL, SAIDALKYD RESIN HAVING A FREE HYDROXYL PERCENTAGE RANGING FROM 0.5 TO 3, AMAXIMUM ACID NUMBER ON THE ORDER OF 25, AND A MAXIMUM GEL TIME ON THEORDER OF 25 SECONDS ON A CURE PLATE MAINTAINED AT A TEMPERATURE OF 190*C., AND BEING SOLUBLE IN SAID ORGANIC SOLVENT.